CN1527834A - Method for producing diphosphines and the use thereof - Google Patents

Method for producing diphosphines and the use thereof Download PDF

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CN1527834A
CN1527834A CNA028073363A CN02807336A CN1527834A CN 1527834 A CN1527834 A CN 1527834A CN A028073363 A CNA028073363 A CN A028073363A CN 02807336 A CN02807336 A CN 02807336A CN 1527834 A CN1527834 A CN 1527834A
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alkyl
phenyl
coo
ring
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CN100402537C (en
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R�����ض�
R·杰克斯特尔
H·克莱因
M·贝勒
ά
K·-D·维泽
C·博格曼
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Evonik Operations GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
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    • C07F9/5027—Polyphosphines
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
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Abstract

The invention relates to a method for producing diphosphines of general formula: R<1>R<2>P-H2C-Ar-CH2-PR<1>R<2>, and to the use thereof in a method for hydroformylating olefins.

Description

The method and the application thereof that prepare two phosphiness
The present invention relates to prepare for example improving one's methods and uses thereof of two (diaryl phosphine methyl) arene compounds of two phosphiness.
Two phosphiness have in industry widely to be used.They play an important role industrial, can be used as the starting raw material of antioxidant, metal extraction agent, fire retardant, soaker, olefin stabilizers, Wittig reagent, particularly can be as the part of transition-metal catalyst.
Can find out the summary of the important homogeneous catalyst that contains the phosphine part, for example: B.Cornils, W.A.Herrmann, Applied Homogeneous Catalysis withOrganometallic Compounds Vol. 1 ﹠amp; 2, VCH, Weinheim, 1996.In phosphine class material, chelating type phosphine (particularly diphosphine class) is very important metal complex part.This is because the diphosphine class can form more stable complex compound with suitable central metal atom, thereby its catalysis characteristics is produced more persistent influence.In known chelating type diphosphine class, two-(diaryl phosphine alkyl)-1,1 '-dinaphthalene as carbonylation reaction catalyst and telomerization catalyzer industrial extremely important.EP 0,653,432, EP 0,673,944 and JP 7939059 put down in writing two (diaryl phosphine alkyl)-1,1 '-preparation method of dinaphthalene: 2,2 '-dimethyl dinaphthalene and bromizating agent reaction make 2,2 '-two (brooethyl)-1,1 '-dinaphthalene, with the reaction of alkyl diphenyl base phospho acid alkyl ester, form corresponding two phosphine oxides by organic dichlorosilane then, reduction obtains product then.This method has many great shortcomings: in order to introduce the phosphorus base on target molecule, at first need the target molecule bromination, could displace bromine atoms with the phosphorus base then.So just need the toxicity bromizating agent of application of expensive, and cause the formation of hyperstoichiometry bromide refuse.The bromination reaction of initial compounds obtains reluctant product mixture usually, and this is because the bromination arylalkyl that forms belongs to the lacrymator of insalubrity.In addition, with diphenyl phosphonic acid alkyl esters substance reaction obtain must be in next procedure the reductive phosphine oxide.Therefore, from 2,2 '-the dimethyl dinaphthalene sets out, and must just can obtain needed part through 4 reactions steps.
Also put down in writing similar synthetic method or partial synthesis method in the literature, these methods have same shortcoming, even (M.E.Jung waits .Tetrahedron Lett.1988,29,6199 also other shortcoming; .Chem.Ber.1974 such as H.J.Bestmann, 2926; .J.Am.Chem.Soc.1988 such as T.Hayashi, 110,8153).
At EP 0,704,449 have put down in writing following method: from 2,2 '-two (brooethyl)-1,1 '-dinaphthalene through its Xiang Ying De phosphonium salt prepare two (diaryl phosphine alkyl)-1,1 of asymmetric replacement '-dinaphthalene.This method also has above-mentioned shortcoming, be not suitable for preparing symmetric two (diaryl phosphine alkyl)-1,1 '-dinaphthalene because need be incorporated into the phosphorus group on the target molecule, and form a large amount of salt refuses with two steps.
For these reasons, need a kind of preparation of exploitation pair (diaryl phosphine (phosphinyl) alkyl)-1,1 '-novel method of dinaphthalene, described novel method should not have above-mentioned shortcoming, simple to operate and safety can obtain required value product by high productivity, and the purity height.
Can achieve the above object by the method for two phosphiness of preparation general formula I,
R 1R 2P-H 2C-Ar-CH 2-PR 1R 2 (I)
It is characterized in that:
A) dimethyl compound of general formula I I,
H 3C-Ar-CH 3 (II)
The amino phosphine halide reaction that replaces with alkali and N-obtains two (amino phosphine (phosphinyl) methyl) compounds of general formula III
R 3R 4P-H 2C-Ar-CH 2-PR 3R 4， (III)
B) compound of formula III that obtains in this way and HCl reaction obtain two (dichloro phosphine methyl) compounds of general formula I V
Cl 2P-H 2C-Ar-CH 2-PCl 2 (IV)
And c) general formula I V compound that obtains in this way and organometallic reagent reaction obtain the target compound of general formula I, wherein R 1And R 2Be independently of one another: aromatics, heteroaromatic or the aliphatic hydrocarbyl of replacement or non-replacement, and can contain a covalent linkage that connects them; Ar is the aromatic group or the heteroaromatic alkyl of replacement or non-replacement; R 3And R 4Aminoalkyl group or the aminoaryl that replaces for N-independently of one another.
Method of the present invention is significant especially method, because the method for the acquisition general formula I part that former prior art is put down in writing always needs by benzyl halogenide intermediate.Method of the present invention can be a raw material with general formula I I compound directly, and high yield and high purity ground obtain two phosphiness.
Can be used for method steps is those CH that can make benzyl with the alkali that general formula I I compound reacts a) 3Group takes off any alkali of proton.The exemplary of these alkali is: lithium alkylide or aryl lithium compounds, for example butyllithium or lithium methide; Alkalimetal hydride or alkaline earth metal hydride be sodium hydride or potassium hydride KH for example; Basic metal in liquefied ammonia or alkaline-earth metal be sodium or potassium for example; The oxyhydroxide or the alkoxide of basic metal or alkaline-earth metal, for example potassium tert.-butoxide that also have basic metal or alkaline-earth metal.
Below by by way of example, with Synthetic 2,2 '-two (diaryl phosphine methyl)-1,1 '-the following reaction scheme of dinaphthalene is to exemplify the method that example explanation the present invention prepares two phosphiness.
The amino phosphine halogenide that replaces as N-in a) at method steps can use alkyl-or muriate, bromide or the iodide of arylamino phosphine, wherein alkyl is the alkyl that is selected from following groups: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, hexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl or different nonyl, and/or these groups can have covalent linkage betwixt; And/or alkylamino is to have the most corresponding aliphatic heterocyclic radical of 6 carbon atoms; And/or aryl is to have the most corresponding aromatic group of 14 carbon atoms; Wherein these groups can have the most nearly 7 substituting groups, and these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
Alkylamino can be aliphatic heterocyclic radical, for example piperidyl or pyrryl; And/or aryl can be for example phenyl, naphthyl or a benzyl of aromatic base.Two (dialkyl amido) phosphine muriates of advantageous applications.For all compounds, the N-P key is necessary can be by acid cleavage.
The more detailed description of general formula I
Radicals R 1And R 2Can be identical or different separately, and can be to have the most nearly aromatic base of 14 carbon atoms, it can have the most nearly 8 substituting groups, and these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2 -(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
And, radicals R 1And R 2Can be identical or different separately, they can be to contain nitrogen, oxygen or sulphur atom five yuan, the assorted aromatic base of hexa-atomic or seven-membered ring on ring, wherein this ring can also condense other aromatics, heteroaromatic and/or aliphatic series ring, and these rings can have the most nearly 7 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2 -(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
In addition, alkyl R 1And R 2Can be identical or different separately, and can be to contain to reach the corresponding cycloalkyl of 10 carbon atoms or the alkyl of acyclic most, it can have the most nearly 7 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2 -(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
In these cases, radicals R 1And R 2Can also interconnect by one or more covalent linkage, thereby form for example xenyl, naphthyl or other loop systems.
Ar can be phenyl, naphthyl, anthryl or phenanthryl, 1,1 '-xenyl unit or 1,1 '-the binaphthylyl unit, it can respectively carry and reach 8 other substituting groups at most, these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4) or one or more condensed phenyl ring.
Perhaps, Ar can be assorted aromatic base, and they contain five yuan, hexa-atomic or seven-membered ring of nitrogen, oxygen or sulphur atom on ring, and wherein this ring can also condense other aromatics, heteroaromatic and/or aliphatic series ring, these rings can have the most nearly 6 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2 -(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
Being used at method steps c) organometallic reagent that general formula I V compound is transformed into the general formula I target compound is: transition metal aromatic hydrocarbons, aliphatic series or aromatic base metal or alkaline earth metal compound.Advantageous applications aliphatic series or aromatics Grignard reagent, zinc alkyl(s) or aryl zincon, alkyl lithium reagents or aryl lithium and/or aryl copper compound.Usually before reaction, independently prepare organometallic reagent, but also can in reaction, prepare organometallic reagent on the spot.
The method steps of each the inventive method a), b) and c) in, applied solvent is an inert organic solvents.According to not exclusively giving an example, the example that can mention is: polar aprotic solvent, aliphatic ether, aromatic hydrocarbons or aliphatic hydrocrbon, fragrance and aliphatic halogenated hydrocarbons, alcohol, ester, acid amides and composition thereof.Naturally, any chemical reaction must not take place with reactant in these solvents.
Preferably, under-80 to 200 ℃ of temperature, carry out method steps a), b) and c); In most of the cases, find that the temperature of-30 to 180 ℃ of application is useful, preferred-20 to 160 ℃ especially.
The special advantage of the inventive method is: do not need to prepare any toxicity benzyl and alkyl bromide, and need not carry out the reaction of reduction-oxidation phosphine class.
Because the stability of general formula III and IV intermediate can not need to carry out for example chromatography of complicated purification process like this through simple these intermediates of crystallization process purifying.Intermediate formula IV compound can make that significant new part obtains with plain mode in many catalytic processs.For the part storehouse of the part for preparing the inventive method, it is more more convenient than currently known methods so far that method of the present invention is considered to.
Can the part of the diphosphine class of the present invention's preparation as metal catalysed reaction particularly be carried out in the hydroformylation reaction of alkene with rhodium.Preferred alkene is octene and butylene, particularly the alkene that those branches are many and/or internal double bonds is many.
Known two phosphiness can be used as part in hydroformylation reaction.Therefore, US4694109 has put down in writing the diphosphine class part with BISBI basic structure, and it is used in the hydroformylation reaction of the alkene with internal double bonds especially, but the document is not discussed the selectivity and the activity of such catalysts of product.
At Angew.Chem.Int.Ed.1999,38, among the 336-338, L.A.van derVeen, P.C.J.Kamer and P.W.N.M.van Leeuwen have reported the XANTPHOS part of modification, its n/i ratio with 9: 1 is transformed into n-nonyl aldehyde to the 2-octene, inversion frequency (=TOF) be 112h -1The definition of TOF is the mol ratio of aldehyde and rhodium per hour after 20-30% conversion.
EP 0653432 has put down in writing the preparation of the diphosphine class that is similar to NAPHOS, and some of them contain fluoro substituents.These parts can be used for the hydroformylation reaction of alkene.The document is not put down in writing the content of relevant selectivity and catalyst activity equally.
In metal complex; the part of the present invention's preparation particularly is similar to wonderful highly selective of fluorine-containing part tool and the highly active catalyzer of NAPHOS; become in the selective hydrogenation formylation reaction of terminal aldehydes at the alkene with internal double bonds, described aldehyde shows the highest known up to now activity.It is summarized in the table 1 among the embodiment.
Equally, two phosphiness that the invention provides following formula are used for the purposes of the hydroformylation reaction of alkene under rhodium catalyst of 3-16 carbon atom as the rhodium part:
Wherein
R＝3，5-C 6H 3F 2；-C 6F 5；2，4，5-C 6H 2F 3，3，5-C 6H 3(CF 3) 2；
3,5-C 6H 3(CH 3) 2Or 3,4,5-C 6H 2F 3Wherein the n/i selectivity of the aldehyde that obtains was preferably greater than 97: 3 greater than 85: 15.
In addition, can use known ligand in the present invention, the inversion frequency that reaches (TOF) is promptly active in 150, is preferably greater than 300.
Hydroformylation reaction can be carried out in a conventional manner, for example according to J.Falbe etc. at " New Syntheses with Carbon Monoxide ", Springer Verlag 1980, the method for 93-123 page or leaf record is carried out.
For alkene, advantageous applications has the alkene of internal double bonds, 2-butylene for example, and refined product I or refined product II, amylene and/or octene are used with pure form of isomer or isomer mixture form under each situation.
Refined product I and refined product II are the C that obtains by cracking reaction 4Mixture, it contains the mixture of butane, butylene and divinyl.
Embodiment:
The following example is in order to describe method of the present invention in detail, rather than present method is limited to embodiment.
1, the usual method of preparation diphosphine class:
Solvent:With the solvent of dry all application of currently known methods, distillation and storage under argon shield.
2,2 a), '-two-{ { [two-(diethylamino)] phosphino-(phosphinyl) }-methyl }-1,1 '-preparation of dinaphthalene
Under slight warm, (the 1.6M hexane, 53mmol) most of solvent is removed in middle decompression from the 33.2ml n-butyllithium solution.In ice bath, after the cooling, add 25ml ether and 7.9ml Tetramethyl Ethylene Diamine (53mmol).Stir and cooling under toward wherein slowly add 5g 2,2 '-dimethyl-1,1 '-solution of dinaphthalene (17.7mmol) in the 30ml ether.Allow reaction mixture at room temperature place 24 hours, place a few hours down at 0 ℃ then.The supernatant liquor that inclines, with hexane wash gained precipitation 2 times, each consumption 25ml.
The scarlet precipitation is mixed with the 50ml normal hexane, be cooled to-70 ℃ then.Under agitation drip the mixture of two (diethylin) phosphines (35.4mmol) of 7.5ml chlorine and 25ml anhydrous n-hexane in this suspension.Described mixture slowly is warmed to room temperature, restir 12 hours.Filtering solution, each extracts precipitation twice with 50ml toluene is counter then.Filtrate merges, and is warmed to 80 ℃ of decompressions (10 then -3Holder) removes chlorine pair (diethylin) phosphines that desolvate with excessive.Resistates contains target product with high purity, just need not be further purified in subsequent reactions and can directly use, for example forming 2,2 '-two [(dichlorophosphinyl)-methyl]-1,1 '-directly use in the reaction of dinaphthalene.
M＝514.59g/mol
31P-NMR(δ[ppm]，C 6D 6)：88.4
1H-NMR (δ [ppm], J[Hz], C 6D 6): 0.45t (=triplet), J=7 (6H); 0.55t, J=7 (6H); (2.5q=quartet), J=7 (4H); 2.6q, J=7 (4H); 2.85d (=bimodal), J=3 (4H); 6.7-7.0m (=multiplet) (6H); 7.6 d, J=8 (2H); 7.7-7.8m (4H).
2,2 b), '-two [(dichlorophosphinyl) methyl]-1,1 '-preparation of dinaphthalene
Step 1a) exist in (referring to top) described reaction residue 2,2 '-two { { [two (diethylin) phosphino-}-methyl-1,1 '-dinaphthalene is dissolved in the 150ml hexane.Under stirring and ice bath cooling, feed gas chlorination hydrogen until this mixture saturated (about 1 hour).Filtering mixt is used twice of 25ml hexane wash resistates then.Merge filtrate, be evaporated to about 50ml.-30 ℃ of following crystallizations go out 2.9g 2,2 '-two [(dichlorophosphinyl) methyl]-1,1 '-dinaphthalene.M＝484.12g/mol
2,2 of the middle application of productive rate: 2.9g (based on step 1a) '-dimethyl-1,1 '-dinaphthalene, its productive rate is 44%).
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：180.00
1H-NMR(δ[ppm]，J[Hz]，CDCl 3)：3.4-3.6m(4H)；7.0d，J＝8.5(2H)；7.2m(2H)；7.43m(2H)；7.6d，J＝8.5(2H)；7.86d，J＝8.3(2H)；7.94d，J＝8.5(2H)
13C-NMR：(δ[ppm]，J[Hz]，CDCl 3)：50.3d， 1J PC＝45.8(P-CH 2)；126.4?d，J＝5.7；126.5d，J＝6.7；126.9s；128.1s；128.4d，J＝2.9；129.0s；129.6d?J＝5；133.0d，J＝16.2；135.0d，J＝2；135.6s.
C) usual method of synthesis type (I) part:
Under argon shield, in the 100ml three-necked bottle, 302mg (12.4mmol) element magnesium is mixed under magnetic stirs with the 10ml absolute ether.At room temperature, by dropping funnel in this mixture slowly (about 1 hour) drip the bromine compounds (being dissolved in the 10ml ether) of the suitable replacement of 12.4mmol.If the Grignard reaction does not begin, in this reaction soln, add a glycol dibromide.When after Grignard is reflected at about 1 hour, finishing (magnesium complete reaction), this solution is transferred in the dropping funnel.
In the 150ml three-necked bottle, the following 1.5g of argon shield (3.1mmol) 2,2 '-two [(dichlorophosphinyl) methyl]-1,1 '-dinaphthalene is dissolved among the absolute THF of 25ml.
At room temperature, this Grignard solution slowly (approximately half an hour in) be added drop-wise to above-mentioned 2,2 '-two [(dichlorophosphinyl) methyl]-1,1 '-dinaphthalene solution in.
Then described solution is heated to boiling, restir made reaction finish in 2 hours.Under argon shield, solution evaporation is extremely done then with Rotary Evaporators.Resistates is dissolved in the toluene of the absolute and/or degassing of 50ml, and adds the water of the 20ml degassing.Stir the mixture half an hour.Separate water, the organic phase dried over sodium sulfate.
Filtering sodium sulfate is used the 25ml toluene wash then, and the reduction vaporization organic phase is to doing.Resistates is gone up through the column chromatography purifying at 40cm post (Kieselgur G60) under argon shield with acetone/EtOH, acetone/MeOH or toluene/hexane recrystallization, wherein uses absolute toluene and makes eluent.
Use the inventive method and prepare following part.
2.) according to 1c) example of part of preparation
A) 2,2 '-two-{ { two-[(2,3,4,5,6-five fluoro-phenyl)]-phosphino-}-methyl }-1,1 '-dinaphthalene
M＝1010.54g/mol
Productive rate: 2.3g (theoretical value 73.4%)
31P-NMR (δ [ppm], J[Hz], CDCl 3) :-46.3qui (=quintet), 3J PF=11
1H-NMR：(δ[ppm]，J[Hz]，CDCl 3)：3.6d，J＝13.8(2H)；4.1d，J＝13.8(2H)；6.3d，J＝8.4(2H)；6.85t，J＝17；7.25t，J＝10.8(2H)；7.65d，J＝8.6(2H)；7.7d，J＝8.1(2H)；7.94d，J＝8.6(2H).
B) 2,2 '-two-{ { two-[(3, the 5-difluorophenyl)]-phosphino-}-methyl }-1,1 '-dinaphthalene
Figure A0280733600141
M＝794.66g/mol
Productive rate: 2.05g (theoretical value 83.2%)
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：-8.99
1H-NMR (δ [ppm], J[Hz], CDCl 3): 3.05-3.1m, (4H); (6.3tt the triplet of=triplet), J=6, J=2.2 (4H); 6.53tt, J=8.9, J=2.2 (2H); 6.65m, (6H); 6.88d, J=8.5 (2H); 7.1tt, J=7, J=1 (2H), 7.2d, J=8.5 (2H); 7.31t, J=7.1 (2H); 7.78t, J=8.5 (4H).
C) 2,2 '-two-{ { two-[(2,4, the 5-trifluorophenyl)]-phosphino-}-methyl }-1,1 '-dinaphthalene
Figure A0280733600142
M＝866.62g/mol
Productive rate: 1.3g (theoretical value 48.4%)
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：-28.8d，J＝23.6；-29.1d，J＝25.0
1H-NMR(δ[ppm]，J[Hz]，CDCl 3)：3.26d，J HH＝14.1(2H)；3.45dd，J HH＝14， 2J PH＝
3.2 (2H); 6.33m (2H), 6.55d; 8.7m (2H); 6.6-6.8m (6H); 6.92td (=doublet
Triplet), J=6.9 J=1.2 (2H); 7.26t, J=7.4 (2H); 7.43dd, J=8.5, J=2.2 (2H); 7.7
d，J＝8.1(2H)；7.76d，J＝7.7(2H).
D) 2,2 '-two-{ { two-[(3, the 5-3,5-dimethylphenyl)]-phosphino-}-methyl }-1,1 '-dinaphthalene
M＝762.95g/mol
Productive rate: 1.9g (theoretical value 80%)
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：-11.4
1H-NMR(δ[ppm]，J[Hz]，CDCl 3)：2.1s，2.2s，2.3s(24H)；3.1dd，J HH＝14.2，J＝2.5
(2H)；3.3dd，J HH＝14.2， 2J PH＝2.2(2H)；6.6d，J＝7.5(4H)；6.9m(6H)，7.1-7.2m
(6H)；7.35dd，J＝8.5，J＝2(2H)；7.4?t，J＝7(2H)；7.8d，J＝8.5(2H)；7.85d，J＝7.9
(2H)
E) 2,2 '-two-{ { two-[(3,4,5-three fluoro-phenyl)]-phosphino-}-methyl }-1,1 '-dinaphthalene
Figure A0280733600161
M＝866.62g/mol
Productive rate: 2.3g (theoretical value 85%)
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：-8.5
1H-NMR(δ[ppm]，J[Hz]，CDCl 3)：3.1m，(2H)；3.05dd，J HH＝13.8， 2J PH＝2.7(2H)；6.3q，J＝6.7(4H)；6.7m(6H)；7.05td，J＝6.7，J＝1.3(2H)；7.3m(4H)；7.8t，J＝8.9(4H).
F) 2,2 '-two-{ { two-[(3,5-trifluoromethyl-phenyl)]-phosphino-}-methyl } }-1,1 '-dinaphthalene
M＝1126.72g/mol
Productive rate: 3.1g (theoretical value 88.7%)
31P-NMR(δ[ppm]，J[Hz]，CDCl 3)：-10.5
1H-NMR(δ[ppm]，J[Hz]，CDCl 3)：3.2m，(4H)；6.95d，J＝8.5(2H)；7.05-7.15m，(4H)，7.25d，J＝4.7(4H)；7.33t，J＝7.3(2H)；7.47d，J＝4.5(4H)；7.65s，(2H)；7.7d，J＝11.1(2H)；7.8d，J＝16.5(4H)
3. the description of hydroformylation reaction
The hydroformylation reaction experiment can be carried out with magnetic driving helical oar stirrer in 100ml autoclave (Parr Co.), or can carry out with magnetic stirrer at 160ml autoclave (Parr Co.).
By No. 1 autoclave test (referring to table 1) the hydroformylation reaction method is described with way of example below.
(8ml 73.0mmol) joins 1.88mg Rh (CO) octane-iso (2ml is as interior mark) and 1-amylene 2Acac (7.3 μ mol) and 44mg part 2.f) in (M:1127,36.5 μ mol) solution in methyl-phenoxide (30ml).After being transferred to mixture in the autoclave, through synthetic gas mode (CO: H 2=1: 1) autoclave is become 5 crust.At first autoclave is heated to 120 ℃ then pressure is slowly increased, then pressure is adjusted to 10 crust.After 16 hours, close autoclave automatically, in ice bath, cool off, be decompressed to normal atmosphere.Directly from autoclave, take out the GC sample, measure then.
Table 1:
Rhodium-catalytic hydroformylation reaction in the presence of the part of the present invention's preparation
Numbering part alkene T (℃) productive rate (%) n/i TOF
1 2f 1-amylene 120 82 96: 4 512
2 2f 2-amylenes 120 68 91: 9 425
3 2f 2-amylenes 100 52 89: 11 325
4 2f 2-butylene 120 66 91: 9 825
5 2f 2-octenes 120 51 86: 14 319
6 2b 1-amylenes 120 78 97: 3 488
7 2b 2-amylenes 120 59 94: 6 369
8 2b 2-amylenes 100 21 95: 5 131
9 2e 1-amylenes 120 83 97: 3 519
10 2e 2-amylenes 120 61 93: 7 381
11 2e 2-amylenes 100 24 94: 6 150
12 2e 2-butylene 120 74 95: 5 925
13 2e 2-octenes 120 48 91: 9 300
14 2e 4-octenes 120 14 66: 34 88
15 2d 1-amylenes 120 76 81: 19 475
16 2d 2-amylenes 120 11 78: 22 69
Use the catalyzer that NAPHOS forms, promptly do not have fluorine-containing substituent parent molecule, as can find out, also show highly selective similarly in following table, but activity is low, this from the TOF value of following table as can be seen.
Table 2 is used the 1-of NAPHOS and the hydroformylation reaction of 2-amylene
Numbering alkene P (crust) T (℃) productive rate n/i TOF
(％)
1 1-amylene 10 120 76 99: 1 475
2 1-amylenes 50 120 88 97: 3 550
3 2-amylenes 10 120 22 89: 11 138
4 2-amylenes 50 120 7 55: 45 44

Claims (12)

1, the method for two phosphiness of preparation general formula I
R 1R 2P-H 2C-Ar-CH 2-PR 1R 2 (I)
It is characterized in that:
A), the dimethyl compound of general formula I I,
H 3C-Ar-CH 3 (II)
The amino phosphine halide reaction that replaces with alkali and N-generates two (amino phosphine methyl) compounds of general formula III,
R 3R 4P-H 2C-Ar-CH 2-PR 3R 4， (III)
B), the compound of formula III that obtains in this way pair (dichloro phosphine methyl) compounds with HCl prepared in reaction general formula I V,
Cl 2P-H 2C-Ar-CH 2-PCl 2 (IV)
And c) general formula I V compound that obtains in this way and organometallic reagent reaction obtain the target compound of general formula I, wherein R 1And R 2Be independently of one another: aromatics, heteroaromatic or the aliphatic hydrocarbyl of replacement or non-replacement, and can contain a covalent linkage that connects them; Ar is the aromatics or the heteroaromatic alkyl of replacement or non-replacement; R 3And R 4Aminoalkyl group or the aminoaryl that replaces for N-independently of one another.
2, the method for claim 1 is characterized in that, radicals R 1And R 2Identical or different, and be to have the most nearly aromatic base of 14 carbon atoms, it can have the most nearly 8 substituting groups, and these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
3, claim 1 or 2 method is characterized in that radicals R 1And R 2Identical or different, they are to contain nitrogen, oxygen or sulphur atom five yuan, the assorted aromatic base of hexa-atomic or seven-membered ring on ring, wherein this ring can also condense other aromatic ring, heteroaromatic rings and/or aliphatic series ring, and these rings can have the most nearly 7 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
4, any one method of claim 1-3 is characterized in that, alkyl R 1And R 2Identical or different, they are to contain to reach the cycloalkyl of 10 carbon atoms or the alkyl of acyclic most, and it can have the most nearly 7 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
5, any one method of claim 1-4 is characterized in that radicals R 1And R 2Between one or more covalent linkage are arranged.
6, any one method of claim 1-5 is characterized in that, Ar be phenyl, naphthyl, anthryl or phenanthryl, 1,1 '-xenyl unit or 1,1 '-the binaphthylyl unit, it can have the most nearly 8 other substituting groups separately, these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4) or one or more condensed phenyl ring.
7, any one method of claim 1-6, it is characterized in that, Ar is assorted aromatic base, it contains five yuan, the hexa-atomic or seven-membered ring that nitrogen, oxygen or sulphur atom are arranged on ring, wherein this ring can also condense other aromatic ring, heteroaromatic rings and/or aliphatic series ring, these rings can have the most nearly 6 substituting groups, and described substituting group is selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
8, any one method of claim 1-7, it is characterized in that, method steps a) in used alkali be lithium alkylide or aryl lithium compounds, alkalimetal hydride or alkaline earth metal hydride, basic metal or alkaline-earth metal, alkali metal hydroxide or alkaline earth metal hydroxides in liquefied ammonia, perhaps alkali metal alkoxide or alkaline-earth metal alkyl oxide.
9, any one method of claim 1-8, it is characterized in that, the amino phosphine halogenide that replaces as N-in a) at method steps uses muriate, bromide or the iodide of alkylamino phosphine or arylamino phosphine, wherein alkyl is the alkyl that is selected from following groups: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, hexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl or different nonyl, and/or these groups can have covalent linkage betwixt; And/or alkylamino is to have the most aliphatic heterocyclic radical of 6 carbon atoms; And/or aryl is to have the most nearly aromatic base of 14 carbon atoms; Wherein these groups can have the most nearly 7 substituting groups, and these substituting groups are selected from: (C 1-C 8)-alkyl, O-alkyl-(C 1-C 8), O-phenyl, phenyl, fluorine, chlorine, CN, COOH, CHO, SO 3H, SO 2-alkyl-(C 1-C 6), SO-alkyl-(C 1-C 6), CF 3, COO-alkyl-(C 1-C 8), COO-phenyl, PO-phenyl 2, the PO alkyl 2-(C 1-C 4), PO 3H 2, PO (O-alkyl-(C 1-C 6)) 2, SO 3-alkyl-(C 1-C 4).
10, any one method of claim 1-9, it is characterized in that, at method steps c) in used organometallic reagent be: transition metal aromatic hydrocarbons, aliphatic series or aromatic base metal or alkaline earth metal compound, aliphatic series or aromatics Grignard reagent, zinc alkyl(s) or aryl zincon, lithium alkylide or aryl lithium and/or aryl copper compound.
11, two phosphiness of following formula carry out the purposes of the method for hydroformylation reaction as the part of rhodium at the alkene that is used for having 3-16 carbon atom in the presence of rhodium catalyst,
R=wherein
3,5-C 6H 3F 2-C 6F 52,4,5-C 6H 2F 3, 3,5-C 6H 3(CF 3) 23,5-C 6H 3(CH 3) 2Or 3,4,5-C 6H 2F 3
Wherein the n/i selectivity of the aldehyde that obtains is greater than 85: 15.
12, the purposes of claim 11 is characterized in that, as alkene, can be the pure form of isomer or as mixture of isomers with butylene, refining product I, refining product II, amylene and/or octene under each situation.
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ES2261674T3 (en) 2006-11-16
KR20030093287A (en) 2003-12-06
MXPA03008430A (en) 2004-01-29
ATE326473T1 (en) 2006-06-15
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